CN105143368A - Antifouling paint composition, antifouling paint film, antifouling substrate, and method for manufacturing antifouling substrate - Google Patents
Antifouling paint composition, antifouling paint film, antifouling substrate, and method for manufacturing antifouling substrate Download PDFInfo
- Publication number
- CN105143368A CN105143368A CN201480022981.8A CN201480022981A CN105143368A CN 105143368 A CN105143368 A CN 105143368A CN 201480022981 A CN201480022981 A CN 201480022981A CN 105143368 A CN105143368 A CN 105143368A
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- CN
- China
- Prior art keywords
- antifouling
- weight
- mentioned
- antifouling paint
- paint compositions
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000003973 paint Substances 0.000 title claims abstract description 77
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- 238000000034 method Methods 0.000 title claims description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 13
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- 239000000178 monomer Substances 0.000 claims abstract description 36
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 14
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- 239000011248 coating agent Substances 0.000 claims description 74
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- 239000002904 solvent Substances 0.000 claims description 25
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Classifications
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- C—CHEMISTRY; METALLURGY
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1675—Polyorganosiloxane-containing compositions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
- B63B—SHIPS OR OTHER WATERBORNE VESSELS; EQUIPMENT FOR SHIPPING
- B63B59/00—Hull protection specially adapted for vessels; Cleaning devices specially adapted for vessels
- B63B59/04—Preventing hull fouling
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/08—Copolymers of styrene
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
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Abstract
Description
技术领域technical field
本发明涉及防污涂料组合物、防污涂膜、防污基材以及防污基材的制造方法。The invention relates to an antifouling coating composition, an antifouling coating film, an antifouling substrate and a method for manufacturing the antifouling substrate.
背景技术Background technique
在船舶、海洋结构物、渔网等中，由于各种海中生物附着在浸渍于海水中的部分，因此使用与有机锡类防污涂料相比毒性低、对环境负荷少的含有含三有机甲硅烷基酯的共聚物的防污涂料。然而，该含有含三有机甲硅烷基酯共聚物的涂膜从浸渍初期开始在某特定期间在海水中以固定的速度溶解，但涂膜的水解速度逐渐变大，如果经过长时间则存在水解速度变得过大而降低耐水性、产生裂纹或剥落的问题。In ships, marine structures, fishing nets, etc., since various marine organisms adhere to the parts immersed in seawater, the use of organic tin-based antifouling paints that contain triorganomethanides has lower toxicity and less environmental load. Antifouling coatings based on copolymers of silyl esters. However, the coating film containing the triorganosilyl ester-containing copolymer dissolves at a constant rate in seawater for a certain period of time from the initial stage of immersion, but the hydrolysis rate of the coating film gradually increases. The hydrolysis rate becomes too large to reduce water resistance and cause cracks or peeling problems.
作为以提高耐裂纹性为目的的防污涂料组合物，提出了含有甲硅烷基聚合物、由Tg为-20℃以下、数均分子量为500～20000的乙烯性不饱和羧酸酯共聚物构成的高分子增塑剂、以及防污化学试剂的防污涂料组合物(专利文献1)；含有水解性甲硅烷基聚合物、相对于该聚合物为不相溶性的聚合物、以及低Tg聚合物的防污涂料组合物(专利文献2)；含有三烷基甲硅烷基聚合物，以及能够与该聚合物相溶的数均分子量为1000～100000的(甲基)丙烯酸酯类共聚物的防污涂料组合物(专利文献3)；在三烷基甲硅烷基聚合物、以及能够与该聚合物相溶的数均分子量为1000～100000的(甲基)丙烯酸酯类共聚物中含有氯化石蜡的防污涂料组合物(专利文献4)等。As an antifouling coating composition for the purpose of improving crack resistance, a silyl polymer is proposed, which is composed of an ethylenically unsaturated carboxylate copolymer having a Tg of -20°C or lower and a number average molecular weight of 500 to 20,000. Polymer plasticizer and antifouling coating composition of antifouling chemical agent (Patent Document 1); containing a hydrolyzable silyl polymer, a polymer that is incompatible with the polymer, and a low Tg polymer antifouling coating composition (Patent Document 2); containing a trialkylsilyl polymer and a (meth)acrylate copolymer with a number average molecular weight of 1,000 to 100,000 that is compatible with the polymer Antifouling coating composition (Patent Document 3); chlorine is contained in a trialkylsilyl polymer and a (meth)acrylate copolymer having a number average molecular weight of 1,000 to 100,000 that is compatible with the polymer An antifouling paint composition made of paraffin wax (Patent Document 4) and the like.
现有技术文献prior art literature
专利文献patent documents
专利文献1：国际公开第2008/105122号Patent Document 1: International Publication No. 2008/105122
专利文献2：日本专利特表2006-503115号公报Patent Document 2: Japanese Patent Application Publication No. 2006-503115
专利文献3：日本专利特开平9-48946号公报Patent Document 3: Japanese Patent Laid-Open No. 9-48946
专利文献4：日本专利特开平9-48947号公报Patent Document 4: Japanese Patent Application Laid-Open No. 9-48947
发明内容Contents of the invention
发明所要解决的技术问题The technical problem to be solved by the invention
然而，专利文献1-4中公开的甲硅烷基聚合物类的防污涂料组合物并不能长期维持涂膜的耐裂纹性的提高效果和防污性能。因此，本发明是鉴于这样的现有技术而产生的课题，其目的在于提供可形成在海水以及淡水中从浸渍初期开始长期不易产生裂纹的涂膜，且能够长期维持优良的涂膜消耗性的甲硅烷基聚合物类的防污涂料组合物。However, the silyl polymer-based antifouling paint compositions disclosed in Patent Documents 1 to 4 cannot maintain the effect of improving the crack resistance of the coating film and the antifouling performance for a long period of time. Therefore, the present invention was made in view of such prior art, and an object of the present invention is to provide a coating film that can form a coating film that is less prone to cracking for a long period of time from the initial stage of immersion in seawater and fresh water, and that can maintain excellent coating film consumption properties for a long period of time. Antifouling coating composition of silyl polymer type.
解决技术问题所采用的技术方案Technical solutions adopted to solve technical problems
本发明人进行认真研究，结果发现通过将含有苯乙烯衍生的构成单元(a-1)以及(甲基)丙烯酸缩水甘油酯衍生的构成单元(a-2)的共聚物(A)混合在含有甲硅烷基酯类聚合物(B)的防污涂料中，可解决上述课题，从而完成了本发明。本发明的技术要点如下所述。As a result of earnest research by the present inventors, it was found that by mixing a copolymer (A) containing a structural unit (a-1) derived from styrene and a structural unit (a-2) derived from glycidyl (meth)acrylate In the antifouling paint of the silyl ester polymer (B), the above-mentioned problems can be solved, and the present invention has been completed. The technical gist of the present invention is as follows.
[1]一种防污涂料组合物，其特征在于，包括[1] An antifouling paint composition, characterized in that, comprising
含有下述通式(a1)：Contains the following general formula (a1):
[化1][chemical 1]
(式中，R为氢原子或甲基)(In the formula, R is a hydrogen atom or a methyl group)
所表示的单体衍生的构成单元(a-1)10～80重量％、(甲基)丙烯酸缩水甘油酯衍生的构成单元(a-2)1～50重量％以及其他的乙烯性不饱和单体衍生的构成单元(a-3)0～89重量％(其中，构成单元(a-1)、(a-2)以及(a-3)的总量为100重量％。)的共聚物(A)，10 to 80% by weight of structural units (a-1) derived from monomers, 1 to 50% by weight of structural units (a-2) derived from glycidyl (meth)acrylate, and other ethylenically unsaturated mono A copolymer ( A),
含有下述通式(b1)：Contains the following general formula (b1):
[化2][Chem 2]
(式中，X为氢原子或羧基，R1为氢原子或甲基，R2～R6为碳数1～6的直链或支链烷基且可相互相同或不同，n为0或1以上的整数。)(In the formula, X is a hydrogen atom or a carboxyl group, R 1 is a hydrogen atom or a methyl group, R 2 to R 6 are linear or branched alkyl groups with 1 to 6 carbons and may be the same or different from each other, n is 0 or 1 or more integers.)
所表示的单体衍生的构成单元(b-1)的聚合物(B)，以及the polymer (B) of the monomer-derived constituent unit (b-1) represented, and
防污剂。antifouling agent.
[2]如上述[1]所述的防污涂料组合物，其中，上述共聚物(A)和上述聚合物(B)的重量比(共聚物(A)的重量/聚合物(B)的重量)为5/95～95/5。[2] The antifouling coating composition as described in [1] above, wherein the weight ratio of the above-mentioned copolymer (A) to the above-mentioned polymer (B) (weight of the copolymer (A)/weight of the polymer (B) Weight) is 5/95 ~ 95/5.
[3]如上述[1]或[2]所述的防污涂料组合物，其中，上述聚合物(B)进一步含有其他的乙烯性不饱和单体衍生的构成单元(b-2)，上述构成单元(b-1)和上述构成单元(b-2)的重量比((b-1)的重量/(b-2)的重量)为30/70～80/20。[3] The antifouling coating composition according to the above [1] or [2], wherein the polymer (B) further contains another structural unit (b-2) derived from an ethylenically unsaturated monomer, and the above The weight ratio (weight of (b-1)/weight of (b-2)) of a structural unit (b-1) and the said structural unit (b-2) is 30/70-80/20.
[4]如上述[1]～[3]中任一项所述的防污涂料组合物，其中，上述聚合物(B)的数均分子量为1000～30000。[4] The antifouling coating composition according to any one of the above [1] to [3], wherein the polymer (B) has a number average molecular weight of 1,000 to 30,000.
[5]如上述[1]～[4]中任一项所述的防污涂料组合物，其中，上述式(b1)所表示的单体(化合物)为三异丙基甲硅烷基(甲基)丙烯酸酯。[5] The antifouling coating composition according to any one of the above [1] to [4], wherein the monomer (compound) represented by the above formula (b1) is triisopropylsilyl (methyl base) acrylate.
[6]如上述[1]～[5]中任一项所述的防污涂料组合物，其中，进一步含有一元羧酸化合物(C)。[6] The antifouling paint composition according to any one of the above [1] to [5], further comprising a monocarboxylic acid compound (C).
[7]如上述[6]所述的防污涂料组合物，其中，上述共聚物(A)以及上述聚合物(B)的总重量和上述一元羧酸化合物(C)的重量比例((共聚物(A)以及聚合物(B)的总重量)/(化合物(C)的重量))为99.9/0.1～30/70。[7] The antifouling coating composition as described in the above [6], wherein the weight ratio of the total weight of the above-mentioned copolymer (A) and the above-mentioned polymer (B) to the above-mentioned monocarboxylic acid compound (C) ((copolymer The total weight of the compound (A) and the polymer (B))/(the weight of the compound (C))) is 99.9/0.1 to 30/70.
[8]如上述[1]～[7]中任一项所述的防污涂料组合物，其中，上述防污剂是选自铜或铜化合物(D)(其中，吡啶硫酮铜除外。)以及有机防污剂(E)的至少1种。[8] The antifouling coating composition according to any one of [1] to [7] above, wherein the antifouling agent is selected from copper or copper compound (D) (excluding copper pyrithione. ) and at least one organic antifouling agent (E).
[9]如上述[1]～[8]中任一项所述的防污涂料组合物，其中，进一步含有选自着色剂(F)、填充颜料(G)、脱水剂(H)、增塑剂(I)、触变剂(J)以及溶剂(K)的1种以上的成分。[9] The antifouling paint composition as described in any one of the above [1] to [8], which further contains a colorant (F), a filler pigment (G), a dehydrating agent (H), a One or more components of a plasticizer (I), a thixotropic agent (J), and a solvent (K).
[10]一种防污涂料组合物，它是上述[1]～[9]中任一项所述的防污涂料组合物，其中，上述共聚物(A)和上述聚合物(B)的总重量相对于该防污涂料组合物的固体成分的总量100重量％，在5重量％以上。[10] An antifouling coating composition, which is the antifouling coating composition described in any one of the above-mentioned [1] to [9], wherein the above-mentioned copolymer (A) and the above-mentioned polymer (B) The total weight is 5% by weight or more relative to 100% by weight of the total solid content of the antifouling paint composition.
[11]如上述[1]～[10]中任一项所述的防污涂料组合物，其中，固体成分含量在70重量％以上，在25℃条件下用斯氏粘度计测定的涂料粘度(KU值)为70～110。[11] The antifouling coating composition according to any one of the above [1] to [10], wherein the solid content is at least 70% by weight, and the coating viscosity is measured at 25° C. (KU value) is 70-110.
[12]一种防污涂膜，其中，由上述[1]～[11]中任一项所述的防污涂料组合物形成。[12] An antifouling coating film formed of the antifouling coating composition according to any one of [1] to [11] above.
[13]一种防污基材，其中，具备基材、和设于该基材的表面上的如上述[12]所述的防污涂膜。[13] An antifouling substrate comprising a substrate and the antifouling coating film according to the above [12] provided on the surface of the substrate.
[14]如上述[13]所述的防污基材，其中，该基材与海水或淡水接触。[14] The antifouling substrate as described in [13] above, wherein the substrate is in contact with seawater or fresh water.
[15]如上述[13]或[14]所述的防污基材，其中，上述基材为选自水中结构物、船舶以及渔具的至少一种。[15] The antifouling base material according to the above [13] or [14], wherein the base material is at least one selected from underwater structures, ships, and fishing gear.
[16]一种防污基材的制造方法，其中，包括在基材上涂覆、或使其含浸上述[1]～[11]中任一项所述的防污涂料组合物的工序。[16] A method for producing an antifouling substrate, comprising the step of coating or impregnating the antifouling coating composition according to any one of [1] to [11] above on the substrate.
发明的效果The effect of the invention
由本发明的防污涂料组合物的形成涂膜，在海水以及淡水中从浸渍初期开始长期不易产生裂纹，且具有优良的消耗持续性、长期防污性也优良。The coating film formed by the antifouling paint composition of the present invention is less prone to cracks for a long period of time from the initial stage of immersion in seawater and fresh water, and has excellent consumption sustainability and long-term antifouling properties.
具体实施方式detailed description
以下，对本发明的防污涂料组合物等进行进一步详细说明。Hereinafter, the antifouling paint composition etc. of this invention are demonstrated in more detail.
[防污涂料组合物][Antifouling coating composition]
本发明的防污涂料组合物含有上述共聚物(A)、聚合物(B)以及防污剂。The antifouling coating composition of this invention contains the said copolymer (A), a polymer (B), and an antifouling agent.
<共聚物(A)><Copolymer (A)>
上述共聚物(A)含有下述通式(a1)：The above-mentioned copolymer (A) contains the following general formula (a1):
[化3][Chem 3]
(式中，R为氢原子或甲基)(In the formula, R is a hydrogen atom or a methyl group)
所表示的单体衍生的构成单元(a-1)、(甲基)丙烯酸缩水甘油酯衍生的构成单元(a-2)，任意地进一步含有其他的乙烯性不饱和单体(以下也称“单体(a3)”。)衍生的构成单元(a-3)。The indicated monomer-derived structural unit (a-1) and glycidyl (meth)acrylate-derived structural unit (a-2) optionally further contain other ethylenically unsaturated monomers (hereinafter also referred to as " Monomer (a3)". )-derived constituent unit (a-3).
上述构成单元(a-1)、上述构成单元(a-2)以及上述构成单元(a-3)分别示于下式。The above-mentioned structural unit (a-1), the above-mentioned structural unit (a-2), and the above-mentioned structural unit (a-3) are shown in the following formulas, respectively.
构成单元(a-1)：Constituent unit (a-1):
[化4][chemical 4]
(式中，R为氢原子或甲基。)(In the formula, R is a hydrogen atom or a methyl group.)
构成单元(a-2)：Constituent unit (a-2):
[化5][chemical 5]
(式中，R为氢原子或甲基。)(In the formula, R is a hydrogen atom or a methyl group.)
构成单元(a-3)：Constituent unit (a-3):
[化6][chemical 6]
(式中，R为氢原子或甲基，A为1价基团。)(In the formula, R is a hydrogen atom or a methyl group, and A is a monovalent group.)
作为上述单体(a3)，例如可例举Examples of the above-mentioned monomer (a3) include
丙烯酸，甲基丙烯酸；Acrylic acid, methacrylic acid;
(甲基)丙烯酸甲酯(将丙烯酸酯以及甲基丙烯酸酯总称为“(甲基)丙烯酸酯”。以下相同。)、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸异丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸环己酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸异辛酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸-3，5，5-三甲基己酯、(甲基)丙烯酸月桂基酯、(甲基)丙烯酸鲸蜡基酯、(甲基)丙烯酸硬脂基酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸-2-羟基乙酯、(甲基)丙烯酸-2-羟基丙酯、(甲基)丙烯酸-4-羟基丁酯、(甲基)丙烯酸-2-羟基-3-苯氧基丙酯、(甲基)丙烯酸-2-甲氧基乙酯、(甲基)丙烯酸-2-乙氧基甲酯、(甲基)丙烯酸-4-甲氧基丁酯、(甲基)丙烯酸甲氧基丙酯、(甲基)丙烯酸丙氧基乙基乙酯、(甲基)丙烯酸-2-丁氧基乙酯、(甲基)丙烯酸异丁氧基乙酯、(甲基)丙烯酸异丁氧基丁基二甘醇酯、(甲基)丙烯酸苯氧基乙酯等(甲基)丙烯酸酯类；Methyl (meth)acrylate (Acrylate and methacrylate are collectively referred to as "(meth)acrylate". The same applies hereinafter.), ethyl (meth)acrylate, propyl (meth)acrylate, (meth)acrylate Base) isopropyl acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, ( Cyclohexyl methacrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 3,5,5-(meth)acrylate Trimethylhexyl, Lauryl (meth)acrylate, Cetyl (meth)acrylate, Stearyl (meth)acrylate, Phenyl (meth)acrylate, Benzyl (meth)acrylate , (meth)acrylate-2-hydroxyethyl, (meth)acrylate-2-hydroxypropyl, (meth)acrylate-4-hydroxybutyl, (meth)acrylate-2-hydroxy-3-benzene Oxypropyl, (meth)acrylate-2-methoxyethyl, (meth)acrylate-2-ethoxymethyl, (meth)acrylate-4-methoxybutyl, (methyl ) methoxypropyl acrylate, propoxyethyl ethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, isobutoxyethyl (meth)acrylate, (methyl) ) (meth)acrylates such as isobutoxybutyl diglycol acrylate, phenoxyethyl (meth)acrylate, etc.;
四乙二醇二丙烯酸酯、三丙二醇二丙烯酸酯、1，3-丁二醇二(甲基)丙烯酸酯，1，4-丁二醇二(甲基)丙烯酸酯、1，6-己二醇二丙烯酸酯、乙二醇二甲基丙烯酸酯、三羟甲基丙烷三丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、二(三羟甲基丙烷)四丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇五丙烯酸酯等多官能性(甲基)丙烯酸酯类；以及Tetraethylene glycol diacrylate, tripropylene glycol diacrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol Alcohol Diacrylate, Ethylene Glycol Dimethacrylate, Trimethylolpropane Triacrylate, Trimethylolpropane Trimethacrylate, Di(trimethylolpropane) Tetraacrylate, Pentaerythritol Triacrylate , pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate and other multifunctional (meth)acrylates; and
乙酸乙烯基酯、异丁基乙烯基醚、乙烯基甲苯、(甲基)丙烯腈、以及丙酸乙烯酯等乙烯基类单体。Vinyl monomers such as vinyl acetate, isobutyl vinyl ether, vinyl toluene, (meth)acrylonitrile, and vinyl propionate.
其中，从长期防污性的观点考虑，进一步优选甲基丙烯酸甲酯、丙烯酸丁酯以及甲基丙烯酸丁酯。Among these, methyl methacrylate, butyl acrylate, and butyl methacrylate are more preferable from the viewpoint of long-term antifouling properties.
通过改变上述构成单元(a-3)的种类或量，可调整上述共聚物(A)以及本发明的防污涂膜的硬度、粘度、玻璃化温度等。The hardness, viscosity, glass transition temperature, etc. of the above-mentioned copolymer (A) and the antifouling coating film of the present invention can be adjusted by changing the type or amount of the above-mentioned structural unit (a-3).
上述构成单元(a-3)可以是全部都由这些单体衍生而来，也可以是大部分(例如95重量％以上)由这些单体衍生而来、少量(例如5重量％以下)由其他单体衍生而来。The above-mentioned structural unit (a-3) may be derived entirely from these monomers, or may be derived mostly (for example, 95% by weight or more) from these monomers, and a small amount (for example, 5% by weight or less) of other monomers. derived from monomers.
上述构成单元(a-1)、上述构成单元(a-2)以及上述构成单元(a-3)分别可以是1种，也可以是2种以上。The said structural unit (a-1), the said structural unit (a-2), and the said structural unit (a-3) may each be 1 type, or may be 2 or more types.
上述共聚物(A)含有苯乙烯衍生的构成单元(a-1)，因此由本发明的防污涂料组合物形成的涂膜等的耐冲击性、耐弯曲性、耐水性、研扫性(日文：研掃性)优良。此外，上述共聚物(A)含有(甲基)丙烯酸缩水甘油酯衍生的构成单元(a-2)，因此由本发明的防污涂料组合物形成的涂膜等与基材的附着性优良。The above-mentioned copolymer (A) contains the structural unit (a-1) derived from styrene, so the impact resistance, bending resistance, water resistance, and rubbing property of the coating film formed by the antifouling paint composition of the present invention, etc. (Japanese : Grinding property) is excellent. In addition, since the above-mentioned copolymer (A) contains the structural unit (a-2) derived from glycidyl (meth)acrylate, the coating film etc. formed from the antifouling coating composition of this invention are excellent in adhesion to a base material.
在防污涂膜由仅含有具柔软性的骨架的树脂构成时，相对于水中摩擦等的外力、粘着作用在防污涂膜上起作用、损害涂膜的研扫性的情况下，上述共聚物(A)的构成单元(a-1)中含有的苯乙烯骨架在侧链上具有苯环，保持了适度的硬度，因此如果是含有含苯乙烯骨架的上述共聚物(A)的防污涂膜，则可发挥物理上的研扫性。另外，苯乙烯骨架中含有的苯环是疏水性的官能团，具有提高防污涂膜的耐水性的效果，起到提高在海水中的涂膜物性的作用。When the antifouling coating film is composed of a resin containing only a flexible skeleton, external forces such as friction in water and adhesion will act on the antifouling coating film to impair the abrasiveness of the coating film. The styrene skeleton contained in the constituent unit (a-1) of the product (A) has a benzene ring on the side chain and maintains moderate hardness. The coating film can exert physical grinding and sweeping properties. In addition, the benzene ring contained in the styrene skeleton is a hydrophobic functional group, which has the effect of improving the water resistance of the antifouling coating film, and plays a role in improving the physical properties of the coating film in seawater.
一般而言，随着在具有水解性基团的树脂中冷拌混合(日文：コールドブレンド)不具有水解性基团的树脂，含有这些树脂的水解性防污涂膜的研扫性下降，在大部分情况下，相对于对导致防污性下降的担忧，上述共聚物(A)具有不影响聚合物(B)的水解性、可提高含有聚合物(B)的防污涂膜的性能的优良特性。In general, as resins without hydrolyzable groups are cold-mixed (Japanese: Cold Blend) with resins having hydrolyzable groups, the scrubbing properties of hydrolyzable antifouling coatings containing these resins decrease. In most cases, the above-mentioned copolymer (A) has the property of improving the performance of the antifouling coating film containing the polymer (B) without affecting the hydrolyzability of the polymer (B) relative to the concern about the decrease of the antifouling property. Excellent characteristics.
通过在含有聚合物(B)的防污涂料组合物中掺合共聚物(A)，可降低涂料组合物的粘度，可实现防污涂料组合物的高固化(日文：ハイソリッド化)。而且，由于可减少VOC量，因此在聚合物(B)之外含有共聚物(A)得无本发明的防污涂料组合物的环境安全性高。By blending the copolymer (A) into the antifouling paint composition containing the polymer (B), the viscosity of the paint composition can be lowered, and high curing (Japanese: high solidification) of the antifouling paint composition can be realized. Furthermore, since the amount of VOC can be reduced, the antifouling paint composition without the present invention containing the copolymer (A) in addition to the polymer (B) has high environmental safety.
由于上述共聚物(A)是通用单体的共聚物，因此能够在环境负荷少且成本低的条件下进行制造。Since the above-mentioned copolymer (A) is a copolymer of general-purpose monomers, it can be produced with little environmental load and at low cost.
共聚物(A)中含有的上述构成单元(a-1)的比例为10～80重量％，优选15～75重量％，进一步优选20～70重量％。在上述比例低于10重量％的过少情况下，由含有该共聚物的防污涂料组合物形成的涂膜等耐冲击性、耐弯曲性、耐水性差。此外，上述比例高于80重量％的过多情况下，在由含有该共聚物以及溶剂的防污涂料组合物形成涂膜时，在干燥过程中容易产生裂纹。The ratio of the said structural unit (a-1) contained in a copolymer (A) is 10 to 80 weight%, Preferably it is 15 to 75 weight%, More preferably, it is 20 to 70 weight%. When the above ratio is too small less than 10% by weight, the coating film formed from the antifouling paint composition containing the copolymer has poor impact resistance, bending resistance, and water resistance. In addition, when the above-mentioned proportion exceeds 80% by weight too much, when a coating film is formed from an antifouling coating composition containing the copolymer and a solvent, cracks are likely to occur during drying.
共聚物(A)中含有的上述构成单元(a-2)的比例为1～50重量％，优选1～40重量％，进一步优选1～30重量％。在上述比例低于1重量％的过少情况下，由本发明的防污涂料组合物形成的涂膜不能得到足够的对基材的附着性，此外，在本发明的防污涂料组合物含有后述的颜料的情况下，不能得到足够的颜料分散性。此外，如果上述比例高于50重量％而过多，则在防污涂料组合物含有颜料的情况下，有时共聚物(A)和颜料的亲和性变得过大而对防污性能造成障碍。The ratio of the said structural unit (a-2) contained in a copolymer (A) is 1-50 weight%, Preferably it is 1-40 weight%, More preferably, it is 1-30 weight%. In the case where the above ratio is too small below 1% by weight, the coating film formed by the antifouling coating composition of the present invention cannot obtain sufficient adhesion to the substrate. In addition, after the antifouling coating composition of the present invention contains In the case of the above-mentioned pigments, sufficient pigment dispersibility cannot be obtained. In addition, if the above-mentioned ratio is too much higher than 50% by weight, when the antifouling coating composition contains a pigment, the affinity between the copolymer (A) and the pigment may become too large, and the antifouling performance may be hindered. .
共聚物(A)中含有的上述构成单元(a-3)的比例是从全部构成单元的比例100重量％中减去上述构成单元(a-1)以及上述构成单元(a-2)的比例后的值，为0～89重量％，优选0～84重量％，进一步优选0～79重量％。The proportion of the above-mentioned structural unit (a-3) contained in the copolymer (A) is obtained by subtracting the proportion of the above-mentioned structural unit (a-1) and the above-mentioned structural unit (a-2) from the ratio of all structural units (100% by weight) The latter value is 0 to 89% by weight, preferably 0 to 84% by weight, more preferably 0 to 79% by weight.
上述共聚物(A)的数均分子量优选1000～50000，更优选1000～30000，进一步优选1000～15000的范围。如果上述数均分子量在50000以下，则即使在本发明的防污涂料组合物含有溶剂的情况下，该组合物的挥发性有机化合物(VOC)量也容易设为400g/L以下，此外，如果上述数均分子量在1000以上，则由本发明的防污涂料组合物形成的涂膜等的耐水性优良。该数均分子量可通过后述的实施例所采用的条件下的GPC测定或类似方法求出。The number average molecular weight of the said copolymer (A) becomes like this. Preferably it is 1,000-50,000, More preferably, it is 1,000-30,000, More preferably, it is the range of 1,000-15,000. If the above-mentioned number average molecular weight is 50000 or less, even if the antifouling coating composition of the present invention contains a solvent, the volatile organic compound (VOC) amount of the composition is easily set to 400 g/L or less. In addition, if When the above-mentioned number average molecular weight is 1000 or more, the water resistance of the coating film and the like formed from the antifouling coating composition of the present invention is excellent. The number average molecular weight can be determined by GPC measurement under the conditions used in Examples described later or by a similar method.
<聚合物(B)><Polymer (B)>
上述聚合物(B)含有下述通式(b1)：The above-mentioned polymer (B) contains the following general formula (b1):
[化7][chemical 7]
(式中，X为氢原子或羧基，R1为氢原子或甲基，R2～R6为碳数1～6的直链或支链烷基且可相互相同或不同，n为0或1以上的整数。)(In the formula, X is a hydrogen atom or a carboxyl group, R 1 is a hydrogen atom or a methyl group, R 2 to R 6 are linear or branched alkyl groups with 1 to 6 carbons and may be the same or different from each other, n is 0 or 1 or more integers.)
所表示的具有三有机甲硅烷基酯基的单体(以下也称为“单体(b1)”。)衍生的构成单元(b-1)，进一步任意地含有其他乙烯性不饱和单体(以下也称为“单体(b2)”。)衍生的构成单元(b-2)。The constituent unit (b-1) derived from the monomer having a triorganosilyl ester group (hereinafter also referred to as "monomer (b1)") further optionally contains other ethylenically unsaturated monomers (Hereafter also referred to as "monomer (b2)".) Derived structural unit (b-2).
作为上述单体(b1)，例如可例举(甲基)丙烯酸三丙基甲硅烷基酯、(甲基)丙烯酸三异丙基甲硅烷基酯、(甲基)丙烯酸三丁基甲硅烷基酯、(甲基)丙烯酸三异丁基甲硅烷基酯、(甲基)丙烯酸三仲丁基甲硅烷基酯、(甲基)丙烯酸三-2-乙基己基甲硅烷基酯、(甲基)丙烯酸丁基二异丙基甲硅烷基酯等(甲基)丙烯酸酯。其中，从耐水解性的观点考虑，优选具有支链烷基的(甲基)丙烯酸烷基甲硅烷基酯，其中特别优选(甲基)丙烯酸三异丙基甲硅烷基酯。上述构成单元(b-1)可以仅为1种，也可以为2种以上。Examples of the monomer (b1) include tripropylsilyl (meth)acrylate, triisopropylsilyl (meth)acrylate, tributylsilyl (meth)acrylate, Triisobutylsilyl (meth)acrylate, Tri-sec-butylsilyl (meth)acrylate, Tri-2-ethylhexylsilyl (meth)acrylate, Butyl diisobutyl (meth)acrylate (meth)acrylates such as propylsilyl ester. Among them, from the viewpoint of hydrolysis resistance, alkylsilyl (meth)acrylates having a branched alkyl group are preferable, and among them, triisopropylsilyl (meth)acrylate is particularly preferable. The said structural unit (b-1) may be only 1 type, and may be 2 or more types.
作为上述单体(b2)，例如可例举Examples of the aforementioned monomer (b2) include
(甲基)丙烯酸；(Methacrylate;
(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸异丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸环己酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸异辛酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸-3，5，5-三甲基己酯、(甲基)丙烯酸月桂基酯、(甲基)丙烯酸鲸蜡基酯、(甲基)丙烯酸硬脂基酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸-2-羟基乙酯、(甲基)丙烯酸-2-羟基丙酯、(甲基)丙烯酸-4-羟基丁酯、(甲基)丙烯酸-2-羟基-3-苯氧基丙酯、(甲基)丙烯酸-2-甲氧基乙酯、(甲基)丙烯酸-2-乙氧基甲酯、(甲基)丙烯酸-4-甲氧基丁酯、(甲基)丙烯酸甲氧基丙酯、(甲基)丙烯酸丙氧基乙基乙酯、(甲基)丙烯酸-2-丁氧基乙酯、(甲基)丙烯酸异丁氧基乙酯、(甲基)丙烯酸异丁氧基丁基二甘醇酯、(甲基)丙烯酸苯氧基乙酯等(甲基)丙烯酸酯类；以及Methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate , 2-ethylhexyl (meth)acrylate, 3,5,5-trimethylhexyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate , Stearyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate , (meth)acrylate-4-hydroxybutyl ester, (meth)acrylate-2-hydroxy-3-phenoxypropyl ester, (meth)acrylate-2-methoxyethyl ester, (meth)acrylic acid -2-ethoxymethyl ester, (meth)acrylate-4-methoxybutyl ester, (meth)acrylate methoxypropyl ester, (meth)acrylate propoxyethyl ethyl ester, (methyl) )-2-butoxyethyl acrylate, isobutoxyethyl (meth)acrylate, isobutoxybutyl diglycol (meth)acrylate, phenoxyethyl (meth)acrylate, etc. (meth)acrylates; and
乙酸乙烯基酯、异丁基乙烯基醚、苯乙烯、乙烯基甲苯、(甲基)丙烯腈、以及丙酸乙烯酯等乙烯基类单体。Vinyl monomers such as vinyl acetate, isobutyl vinyl ether, styrene, vinyl toluene, (meth)acrylonitrile, and vinyl propionate.
上述构成单元(b-1)可以仅为1种，也可以为2种以上。The said structural unit (b-1) may be only 1 type, and may be 2 or more types.
上述构成单元(b-2)可以是全部都由这些单体衍生而来，也可以是大部分(例如95重量％以上)由这些单体衍生而来、少量(例如5重量％以下)由其他单体衍生而来。The above-mentioned structural unit (b-2) may be derived entirely from these monomers, or may be derived mostly (for example, 95% by weight or more) from these monomers, and a small amount (for example, 5% by weight or less) of other monomers. derived from monomers.
聚合物(B)中含有的上述构成单元(b-1)的比例优选30～80重量％，更优选40～80重量％，进一步优选45～75重量％。此外，聚合物(B)中含有的上述构成单元(b-2)的比例优选20～70重量％，更优选20～60重量％，进一步优选25～55重量％。如果构成单元的比例在上述的范围内，则由本发明的防污涂料组合物形成的防污涂膜等消耗性优良，长期的防污性优良。The proportion of the above-mentioned structural unit (b-1) contained in the polymer (B) is preferably 30 to 80% by weight, more preferably 40 to 80% by weight, and still more preferably 45 to 75% by weight. Moreover, the ratio of the said structural unit (b-2) contained in a polymer (B) becomes like this. Preferably it is 20 to 70 weight%, More preferably, it is 20 to 60 weight%, More preferably, it is 25 to 55 weight%. When the ratio of the constituent units is within the above range, the antifouling coating film formed from the antifouling coating composition of the present invention has excellent consumption properties and long-term antifouling properties.
上述聚合物(B)的数均分子量优选1000～50000，更优选1000～30000，进一步优选1000～15000的范围。如果上述数均分子量在50000以下，则即使在本发明的防污涂料组合物含有溶剂的情况下，该组合物的挥发性有机化合物(VOC)量也容易设为400g/L以下，此外，如果上述数均分子量在1000以上，则由本发明的防污涂料组合物形成的涂膜等的耐水性优良。该数均分子量可通过后述的实施例所采用的条件下的GPC测定或类似方法求出。The number average molecular weight of the polymer (B) is preferably 1,000 to 50,000, more preferably 1,000 to 30,000, and still more preferably 1,000 to 15,000. If the above-mentioned number average molecular weight is 50000 or less, even if the antifouling coating composition of the present invention contains a solvent, the volatile organic compound (VOC) amount of the composition is easily set to 400 g/L or less. In addition, if When the above-mentioned number average molecular weight is 1000 or more, the water resistance of the coating film and the like formed from the antifouling coating composition of the present invention is excellent. The number average molecular weight can be determined by GPC measurement under the conditions used in Examples described later or by a similar method.
<聚合物(共聚物)的制造方法><Manufacturing method of polymer (copolymer)>
作为本发明的共聚物(A)以及聚合物(B)的制造方法，没有特别的限定，例如可例举将上述单体按照上述的构成单元的比例进行混合，在聚合引发剂的存在下，在60～200℃左右的温度下使其聚合的方法。The method for producing the copolymer (A) and polymer (B) of the present invention is not particularly limited, for example, mixing the above-mentioned monomers according to the ratio of the above-mentioned constituent units, and in the presence of a polymerization initiator, A method of polymerizing at a temperature of about 60 to 200°C.
作为上述聚合引发剂，例如可使用2，2'-偶氮二异丁腈、2，2'-偶氮二-2-甲基丁腈、2，2'-偶氮二-2，4-二甲基戊腈、4，4'-偶氮二-4-氰基戊酸等偶氮类自由基聚合引发剂或过氧-2-乙基己酸叔丁酯、过氧苯甲酸叔丁酯、过氧化二叔丁基等的过氧化物类自由基聚合引发剂等。这些可单独1种或将2种以上组合使用。As the above-mentioned polymerization initiator, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, 2,2'-azobis-2,4- Azo radical polymerization initiators such as dimethylvaleronitrile, 4,4'-azobis-4-cyanovaleric acid, or tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxybenzoate Peroxide-based radical polymerization initiators such as esters and di-tert-butyl peroxide. These can be used individually by 1 type or in combination of 2 or more types.
作为分别制造共聚物(A)以及共聚物(B)的方法，可例举溶液聚合、悬浊聚合、加压聚合等，从通用性高的方面考虑，优选使用通常的有机溶剂在常压下进行的溶液聚合。As a method for separately producing the copolymer (A) and the copolymer (B), solution polymerization, suspension polymerization, pressure polymerization, etc. may be mentioned, and from the viewpoint of high versatility, it is preferable to use a common organic solvent under normal pressure performed solution polymerization.
作为用于上述溶液聚合的溶剂，例如可例举甲苯、二甲苯、乙苯、均三甲苯等芳香族烃类溶剂，乙酸丁基酯等酯类溶剂，甲基异丁基酮，甲基氨基酮等酮类溶剂等，其中，作为防污涂料组合物的溶剂从通用性高的方面考虑，特别优选二甲苯。这些溶剂可单独1种或将2种以上组合使用。As the solvent used for the above-mentioned solution polymerization, for example, aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, and mesitylene, ester solvents such as butyl acetate, methyl isobutyl ketone, methyl amino Among the ketone-based solvents such as ketones, xylene is particularly preferred as a solvent for the antifouling paint composition because of its high versatility. These solvents may be used alone or in combination of two or more.
考虑到防污涂料组合物的长期储藏稳定性，优选共聚物(A)和聚合物(B)相溶。作为确认它们的相溶性的方法，可例举以下的手法。In view of the long-term storage stability of the antifouling coating composition, it is preferable that the copolymer (A) and the polymer (B) are compatible. As a method of confirming these compatibility, the following methods are mentioned.
(相溶性的确认法)(compatibility confirmation method)
将共聚物(A)和聚合物(B)以重量比1∶1的比例进行混合，在其中加入二甲苯使共聚物(A)以及聚合物(B)的固体成分的总重量达到30重量％，将其充分搅拌。接着静置30分钟后，如果混合溶液透明或白浊则判断为相溶，如果分离为2层则判断为不相溶。The copolymer (A) and the polymer (B) are mixed in a ratio of 1:1 by weight, and xylene is added therein so that the total weight of the solid content of the copolymer (A) and the polymer (B) reaches 30% by weight , stir it well. Then, after standing still for 30 minutes, if the mixed solution was transparent or cloudy, it was judged to be compatible, and if it separated into two layers, it was judged to be incompatible.
<防污剂><Anti-fouling agent>
作为上述防污剂，可例举铜或铜化合物(D)、有机防污剂(E)等。Copper or a copper compound (D), an organic antifouling agent (E), etc. are mentioned as said antifouling agent.
(铜或铜化合物(D))(copper or copper compound (D))
作为上述铜，可例举铜粉。此外，作为上述铜化合物可例举氧化亚铜、硫氰酸铜、白铜等，特别优选氧化亚铜、硫氰酸铜。此外，本发明中，吡啶硫酮铜不属于铜化合物(D)，被分类为有机防污剂(E)。上述铜或铜化合物(D)的量相对于本发明的防污涂料组合物的固体成分的总量100重量％，优选0.1～90重量％，更优选1～80重量％。上述铜化合物从涂料的储藏稳定性的观点考虑，优选基于其总重量，作为杂质不含有2重量％以上的金属铜。Copper powder is mentioned as said copper. Moreover, cuprous oxide, copper thiocyanate, cupronickel etc. are mentioned as said copper compound, Cuprous oxide and copper thiocyanate are especially preferable. In addition, in the present invention, copper pyrithione does not belong to the copper compound (D), and is classified as an organic antifouling agent (E). The amount of the copper or copper compound (D) is preferably 0.1 to 90% by weight, more preferably 1 to 80% by weight, based on 100% by weight of the total solid content of the antifouling paint composition of the present invention. From the viewpoint of the storage stability of the paint, the copper compound preferably does not contain 2% by weight or more of metallic copper as an impurity based on the total weight thereof.
另外，上述固体成分(加热残留成分)的值为用以下的方法或类似方法测定时的值。对于成分(D)以外的成分也相同。In addition, the value of the said solid content (heating residual content) is the value at the time of measuring by the following method or a similar method. The same applies to components other than the component (D).
[固体成分(加热残留成分)的含有率的测定条件][Measurement conditions for the content rate of solid content (heating residual content)]
在直径6cm的铝试验皿中量取防污涂料组合物X1(g)，将其均匀涂开。在160℃的恒温槽内将其加热1小时去除挥发成分。量取得到的不挥发成分的重量(X2(g))，由下述式算出固体成分(加热残留成分)的含有率。Measure the antifouling coating composition X 1 (g) in an aluminum test dish with a diameter of 6 cm, and spread it evenly. It was heated in a constant temperature bath at 160° C. for 1 hour to remove volatile components. The weight (X 2 (g)) of the obtained non-volatile matter was measured, and the content rate of the solid content (heating residual content) was calculated from the following formula.
固体成分(加热残留成分)的含有率(％)＝X2÷X1×100Content rate (%) of solid content (heating residual content) = X 2 ÷ X 1 × 100
(有机防污剂(E))(Organic antifouling agent (E))
本发明的防污涂料组合物从提高耐粘液性、耐藻类性的观点考虑，可含有有机防污剂(E)。作为其他有机防污剂(E)，可含有吡啶硫酮铜、吡啶硫酮锌等金属吡啶硫酮类，4，5-二氯-2-正辛基-4-异噻唑啉-3-酮、4-溴-2-(4-氯苯基)-5-(三氟甲基)-1H-吡咯-3-腈、吡啶三苯基硼、N，N-二甲基二氯苯脲、2，4，6-三氯苯基马来酰亚胺、2-甲硫基-4-叔丁基氨基-6-环丙基S三嗪、(+/-)-4-[1-(2，3-二甲基苯基)乙基]-1H-咪唑、2，4，5，6-四氯间苯二腈、双[二甲基二硫代氨基甲酰基亚乙基双(二硫代氨基甲酸)锌](日文：ビスジメチルジチオカルバモイルジンクエチレンビスジチオカーバメート)、氯甲基-正辛基二硫醚、N，N'-二甲基-N'-苯基-(N-氟代二氯甲硫基)磺酰胺、N，N'-二甲基-N'-甲苯基-(N-氟代二氯甲硫基)磺酰胺、二硫代四烷基秋兰姆、二甲基二硫代氨基甲酸锌、亚乙基二硫代氨基甲酸锌、2，3-二氯-N-(2'，6'-二乙基苯基)马来酰亚胺、2，3-二氯-N-(2'-乙基-6'-甲基苯基)马来酰亚胺等。其中，特别优选吡啶硫酮铜、吡啶硫酮锌等金属吡啶硫酮类，4，5-二氯-2-正辛基-4-异噻唑啉-3-酮、4-溴-2-(4-氯苯基)-5-(三氟甲基)-1H-吡咯-3-腈、吡啶三苯基硼、N，N-二甲基二氯苯脲、2-甲硫基-4-叔丁基氨基-6-环丙基S三嗪、双[二甲基二硫代氨基甲酰基亚乙基双(二硫代氨基甲酸)锌]。上述有机防污剂(E)的量相对于本发明的防污涂料组合物的固体成分(加热残留成分)的总量100重量％，优选0.1～90重量％，更优选0.5～80重量％。The antifouling paint composition of the present invention may contain an organic antifouling agent (E) from the viewpoint of improving slime resistance and algae resistance. As other organic antifouling agents (E), metal pyrithiones such as copper pyrithione and zinc pyrithione may be contained, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one , 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile, pyridinetriphenylboron, N,N-dimethyldichlorophenylurea, 2,4,6-Trichlorophenylmaleimide, 2-methylthio-4-tert-butylamino-6-cyclopropyl S-triazine, (+/-)-4-[1-( 2,3-Dimethylphenyl)ethyl]-1H-imidazole, 2,4,5,6-tetrachloroisophthalonitrile, bis[dimethyldithiocarbamoylethylene bis(di Thiocarbamate) Zinc] (Japanese: ビスジメチチルジチオカルバモイルジンクエチレンビスジチオカーバメート), chloromethyl-n-octyl disulfide, N, N'-dimethyl-N'-phenyl-(N- Fluorodichloromethylthio)sulfonamide, N,N'-dimethyl-N'-tolyl-(N-fluorodichloromethylthio)sulfonamide, dithiotetraalkylthiuram, Zinc dimethyldithiocarbamate, zinc ethylenedithiocarbamate, 2,3-dichloro-N-(2',6'-diethylphenyl)maleimide, 2, 3-dichloro-N-(2'-ethyl-6'-methylphenyl)maleimide, etc. Among them, metal pyrithiones such as copper pyrithione and zinc pyrithione, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 4-bromo-2-( 4-Chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile, pyridinetriphenylboron, N,N-dimethyldichlorophenylurea, 2-methylthio-4- tert-butylamino-6-cyclopropyl triazine, bis[dimethyldithiocarbamoylethylenebis(dithiocarbamate)zinc]. The amount of the above-mentioned organic antifouling agent (E) is preferably 0.1 to 90% by weight, more preferably 0.5 to 80% by weight based on 100% by weight of the total solid content (residual heating content) of the antifouling coating composition of the present invention.
<其他成分><other ingredients>
本发明的防污涂料组合物从调整涂膜消耗性的观点考虑，优选含有一元羧酸化合物(C)。作为一元羧酸化合物(C)，可例举脂肪族或脂环式一元羧酸、所述一元羧酸的衍生物或金属盐等。其重量比例(上述共聚物(A)和上述聚合物(B)的总重量/上述一元羧酸化合物(C)的重量)优选99.9/0.1～30/70，进一步优选95/5～40/60。The antifouling paint composition of the present invention preferably contains a monocarboxylic acid compound (C) from the viewpoint of adjusting coating film consumption. The monocarboxylic acid compound (C) may, for example, be an aliphatic or alicyclic monocarboxylic acid, a derivative or a metal salt of the monocarboxylic acid, or the like. The weight ratio (the total weight of the above-mentioned copolymer (A) and the above-mentioned polymer (B)/the weight of the above-mentioned monocarboxylic acid compound (C)) is preferably 99.9/0.1 to 30/70, more preferably 95/5 to 40/60 .
作为上述一元羧酸的例，可例举松香、松香衍生物、环烷酸、环烯基羧酸、二环烯基羧酸、叔碳酸、三甲基异丁烯基环己烯羧酸、新癸酸、异壬酸、硬脂酸、羟基硬脂酸以及水杨酸以及它们的金属盐，其中特别优选松香、松香衍生物、环烷酸、叔碳酸、三甲基异丁烯基环己烯羧酸以及它们的金属盐。Examples of the above-mentioned monocarboxylic acid include rosin, rosin derivatives, naphthenic acid, cycloalkenyl carboxylic acid, bicycloalkenyl carboxylic acid, tertiary carbonic acid, trimethylisobutenylcyclohexene carboxylic acid, neodecyl acid, isononanoic acid, stearic acid, hydroxystearic acid and salicylic acid and their metal salts, among which rosin, rosin derivatives, naphthenic acid, tertiary carbonic acid, trimethylisobutenylcyclohexenecarboxylic acid are particularly preferred and their metal salts.
本发明的防污涂料组合物也可进一步含有着色剂(F)、填充颜料(G)、脱水剂(H)、增塑剂(I)、触变剂(防流挂·防沉降剂)(J)、溶剂(K)中的任意1种以上。The antifouling paint composition of the present invention may further contain a colorant (F), an extender pigment (G), a dehydrating agent (H), a plasticizer (I), a thixotropic agent (anti-sagging and anti-settling agent) ( Any one or more of J) and the solvent (K).
作为上述着色颜料(F)，可以使用目前公知的有机类、无机类的各种颜料或染料。作为有机类颜料，例如可例举炭黑、萘酚红、酞菁蓝。作为无机类颜料，例如可以例举氧化铁红、重晶石粉、钛白、黄色氧化铁。如果本发明的防污涂料组合物含有着色剂(F)，则从可任意调节由该组合物得到的防污涂膜的色相的方面考虑，是优选的。上述着色剂(F)的含量相对于本发明的防污涂料组合物的固体成分(加热残留成分)的总量100重量％，优选0.01～70重量％，更优选0.01～50重量％。As the above-mentioned coloring pigment (F), various conventionally known organic and inorganic pigments or dyes can be used. Examples of organic pigments include carbon black, naphthol red, and phthalocyanine blue. Examples of inorganic pigments include red iron oxide, barite powder, titanium white, and yellow iron oxide. When the antifouling paint composition of the present invention contains a colorant (F), it is preferable from the viewpoint that the hue of the antifouling paint film obtained from the composition can be adjusted arbitrarily. The content of the colorant (F) is preferably 0.01 to 70% by weight, more preferably 0.01 to 50% by weight, based on 100% by weight of the total solid content (residual heating content) of the antifouling paint composition of the present invention.
作为上述体质颜料(G)，例如可例举氧化锌、滑石、二氧化硅、云母、粘土、钾长石、玻璃碎片、还可作为防沉淀剂使用的碳酸钙、高岭土、矾土白、还可作为消光剂使用的白炭墨、氢氧化铝、碳酸镁、碳酸钡、硫酸钡，其中优选选自滑石、二氧化硅、云母、粘土、碳酸钙、高岭土、硫酸钡、钾长石的填充颜料。这些填充颜料从可调节由该组合物得到的防污涂膜的成膜性、耐水性、光泽性等的方面考虑，优选单独使用1种或将2种以上组合使用。上述填充颜料(G)的含量相对于本发明的防污涂料组合物的固体成分(加热残留成分)的总量100重量％，优选0.1～90重量％，更优选1～75重量％。Examples of the extender pigment (G) include zinc oxide, talc, silica, mica, clay, potassium feldspar, glass shards, calcium carbonate that can also be used as an anti-settling agent, kaolin, alumina white, or White carbon ink, aluminum hydroxide, magnesium carbonate, barium carbonate, barium sulfate that can be used as a matting agent, among which filler pigments selected from talc, silicon dioxide, mica, clay, calcium carbonate, kaolin, barium sulfate, potassium feldspar are preferred . These extender pigments are preferably used alone or in combination of two or more from the viewpoint that the film-forming properties, water resistance, and gloss properties of the antifouling coating film obtained from the composition can be adjusted. The content of the extender pigment (G) is preferably 0.1 to 90% by weight, more preferably 1 to 75% by weight, based on 100% by weight of the total solid content (heating residual content) of the antifouling paint composition of the present invention.
防污涂膜优选体现出从浸水初期开始长期以固定的比例消耗的行为。在消耗性不固定的情况下，涂膜的更新性突然上升，防污涂膜提前消失、或涂膜的更新性受损而发生污损的风险提高。此外，有根据涂装的位置而防污性能产生差异、不能发挥稳定的防污性能之虞。The antifouling coating film preferably exhibits a behavior of being consumed at a constant rate over a long period of time from the initial stage of water immersion. When the consumption is not constant, the renewability of the coating film suddenly increases, the antifouling coating film disappears early, or the renewability of the coating film is impaired to increase the risk of fouling. In addition, there is a possibility that the antifouling performance may vary depending on the position of the coating, and stable antifouling performance may not be exhibited.
在本发明的防污涂料组合物含有颜料的情况下，共聚物(A)的苯乙烯骨架中含有的苯环对疏水性的颜料进行吸附，(甲基)丙烯酸缩水甘油酯衍生的构成单元(a-2)介由缩水甘油基对该涂料组合物中含有的亲水性颜料进行吸附。通过这样的对颜料成分的吸附效果，共聚物(A)良好地分散在该涂料组合物中。通过该效果，由在聚合物(B)之外含有共聚物(A)的防污涂料组合物形成的涂膜具有均匀的组成，能够以固定的速度消耗。When the antifouling paint composition of the present invention contains a pigment, the benzene ring contained in the styrene skeleton of the copolymer (A) adsorbs the hydrophobic pigment, and the constituent unit derived from glycidyl (meth)acrylate ( a-2) The hydrophilic pigment contained in the coating composition is adsorbed through the glycidyl group. The copolymer (A) is favorably dispersed in the coating composition by such an adsorption effect on the pigment component. Due to this effect, the coating film formed from the antifouling coating composition containing the copolymer (A) in addition to the polymer (B) has a uniform composition and can be consumed at a constant rate.
作为上述脱水剂(H)，优选例举作为无机类脱水剂的合成沸石以及无水石膏·半水石膏，作为有机类脱水剂的四甲氧基硅烷、四乙氧基硅烷、四丁氧基硅烷、四苯氧基硅烷、甲基三乙氧基硅烷、二甲基二乙氧基硅烷、三甲基乙氧基硅烷等烷氧基硅烷类或作为其缩合物的聚烷氧基硅烷类，原甲酸甲酯、原甲酸乙酯等原甲酸烷基酯类。由于该防污涂料组合物的储藏时生成水分，因此以防止水解树脂的分解而引起的涂料凝胶化等为目的而使用这些脱水剂(H)。上述脱水剂(H)的含量相对于本发明的防污涂料组合物的固体成分(加热残留成分)的总量100重量％，优选0.01～50重量％，更优选0.01～30重量％。As the dehydrating agent (H), preferred examples include synthetic zeolite and anhydrite/hemihydrate as inorganic dehydrating agents, and tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane as organic dehydrating agents. Alkoxysilanes such as silane, tetraphenoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, or polyalkoxysilanes that are condensates thereof , methyl orthoformate, ethyl orthoformate and other alkyl orthoformate. Since moisture is generated during storage of the antifouling paint composition, these dehydrating agents (H) are used for the purpose of preventing gelation of the paint due to decomposition of the hydrolyzed resin, and the like. The content of the dehydrating agent (H) is preferably 0.01 to 50% by weight, more preferably 0.01 to 30% by weight, based on 100% by weight of the total solid content (remaining content after heating) of the antifouling coating composition of the present invention.
作为上述增塑剂(I)，可例举氯化石蜡(也称为“氯化链烷烃”。)、石油树脂类、酮树脂、TCP(磷酸三甲苯酯)、聚乙烯基乙基醚、邻苯二甲酸二烷基酯等，其中优选氯化石蜡、石油树脂类以及酮树脂。这些增塑剂可以单独使用1种，也可以2种以上组合使用。如果本发明的防污涂料组合物含有增塑剂(I)，则从进一步提高由该防污涂料组合物形成的涂膜(防污涂膜)的耐裂纹性的方面考虑，是优选的。Examples of the above plasticizer (I) include chlorinated paraffins (also referred to as "chlorinated paraffins"), petroleum resins, ketone resins, TCP (tricresyl phosphate), polyvinyl ethyl ether, Dialkyl phthalates and the like, among which chlorinated paraffins, petroleum resins, and ketone resins are preferable. These plasticizers may be used alone or in combination of two or more. If the antifouling coating composition of the present invention contains the plasticizer (I), it is preferable from the viewpoint of further improving the crack resistance of the coating film (antifouling coating film) formed from the antifouling coating composition.
作为上述氯化石蜡，可以是直链状或具有支链，在室温下可以是液状或固体(粉体)，优选使用1个分子中的平均碳数通常为8～30、优选10～26的氯化石蜡，优选使用数均分子量通常为200～1200、优选300～1100，粘度通常在1以上(泊/25℃)、优选1.2以上(泊/25℃)，比重为1.05～1.80/25℃、优选1.10～1.70/25℃的氯化石蜡。如果使用这样的平均碳数的氯化石蜡，则可以使用所得的防污涂料组合物来形成开裂、剥离少的涂膜。As the above-mentioned chlorinated paraffin, it may be linear or branched, and may be liquid or solid (powder) at room temperature, and the average carbon number in one molecule is usually 8-30, preferably 10-26. Chlorinated paraffin, the number average molecular weight is preferably 200-1200, preferably 300-1100, the viscosity is usually above 1 (poise/25°C), preferably above 1.2 (poise/25°C), and the specific gravity is 1.05-1.80/25°C , Preferably chlorinated paraffin at 1.10-1.70/25°C. When the chlorinated paraffin with such an average carbon number is used, the resulting antifouling coating composition can be used to form a coating film with less cracking and peeling.
此外，该氯化石蜡的氯化率(氯含量)优选35～75％，进一步优选35～65％。如果使用这样的氯化率的氯化石蜡，则可以使用所得的防污涂料组合物来形成开裂、剥离少的涂膜。In addition, the chlorination rate (chlorine content) of the chlorinated paraffin is preferably 35 to 75%, more preferably 35 to 65%. When chlorinated paraffins having such a chlorination rate are used, the resulting antifouling coating composition can be used to form a coating film with less cracking and peeling.
作为上述氯化石蜡，如果是市售品，可例举东曹株式会社(東ソー(株))制的“TOYOPARAX150”、“TOYOPARAXA-70”等。As the said chlorinated paraffin, if it is a commercial item, "TOYOPARAX150" and "TOYOPARAXA-70" by Tosoh Corporation (Tosoh Corporation) etc. are mentioned.
此外，作为上述石油树脂类，例如可例举C5类、C9类、苯乙烯类、二环戊二烯类或它们的加氢物，如果是市售品，可举例日本瑞翁株式会社(日本ゼオン)制的“Quintone1500”、“Quintone1700”等。In addition, as the above-mentioned petroleum resins, for example, C5-based, C9-based, styrene-based, dicyclopentadiene-based, or their hydrogenated products can be mentioned, and if they are commercially available, Nippon Zeon Co., Ltd. (Japan "Quintone 1500" and "Quintone 1700" manufactured by ゼオン).
上述增塑剂(I)的含量相对于本发明的防污涂料组合物的固体成分(加热残留成分)的总量100重量％，优选0.01～50重量％，更优选0.01～30重量％。The content of the above-mentioned plasticizer (I) is preferably 0.01 to 50% by weight, more preferably 0.01 to 30% by weight, based on 100% by weight of the total solid content (remaining content after heating) of the antifouling coating composition of the present invention.
作为上述触变剂(防流挂·防沉降剂)(J)，可例举Examples of the above-mentioned thixotropic agent (anti-sag and anti-settling agent) (J) include
选自有机粘土类Al、Ca、Zn的胺盐、硬脂酸盐、卵磷脂盐、烷基磺酸盐的盐类(j1)；Salts (j1) selected from amine salts, stearates, lecithin salts, and alkylsulfonates of organoclays Al, Ca, and Zn;
选自聚乙烯蜡、酰胺蜡、氢化蓖麻油蜡类、聚酰胺蜡类的有机蜡类(j2)；Organic waxes (j2) selected from polyethylene waxes, amide waxes, hydrogenated castor oil waxes, polyamide waxes;
两者((j1)以及(j2))的混合物(j3)；以及a mixture (j3) of both ((j1) and (j2)); and
合成微粉二氧化硅(j4)。Synthetic micronized silica (j4).
这些触变剂可以单独使用1种，也可以2种以上组合使用。触变剂(防流挂·防沉降剂)(J)以防止该防污涂料组合物的储藏时的上述铜或铜化合物(D)、有机防污剂(E)、着色剂(F)、填充颜料(G)、脱水剂(H)等固形材料的沉淀，提高涂装时的涂装作业性的目的来使用。上述触变剂(防流挂·防沉降剂)(J)的含量相对于本发明的防污涂料组合物的固体成分(加热残留成分)的总量100重量％，优选0.01～50重量％，更优选0.01～30重量％。These thixotropic agents may be used alone or in combination of two or more. Thixotropic agent (anti-sagging and anti-settling agent) (J) to prevent the above-mentioned copper or copper compound (D), organic antifouling agent (E), colorant (F), It is used for the purpose of filling the precipitation of solid materials such as pigment (G) and dehydrating agent (H) and improving the painting workability during painting. The content of the above-mentioned thixotropic agent (anti-sag and anti-settling agent) (J) is preferably 0.01 to 50% by weight relative to 100% by weight of the total solid content (heating residual content) of the antifouling coating composition of the present invention, More preferably, it is 0.01 to 30% by weight.
本发明的防污涂料组合物为了提高共聚物(A)等对聚合物(B)的分散性、调整该组合物的粘度，可根据需要，含有水或有机溶剂等溶剂(K)。上述溶剂(K)可以是在制备共聚物(A)或聚合物(B)时使用的溶剂，也可以是将共聚物(A)以及聚合物(B)和根据需要使用的其他成分混合、制备本发明的防涂料组合物时另外添加的溶剂。The antifouling paint composition of the present invention may optionally contain a solvent (K) such as water or an organic solvent in order to improve the dispersibility of the copolymer (A) and the like to the polymer (B) and to adjust the viscosity of the composition. The above-mentioned solvent (K) may be the solvent used in the preparation of the copolymer (A) or the polymer (B), or may be prepared by mixing the copolymer (A), the polymer (B) and other components used as necessary, and An additional solvent is added to the anti-coating composition of the present invention.
作为上述有机溶剂，例如可例举二甲苯、甲苯、乙苯等芳香族类有机溶剂；甲基乙基酮、甲基异丁基酮、环己酮等酮类；乙醇、异丙醇、丁醇、异丁醇等脂肪族(碳数1～10，优选2～5左右)的一元醇类；乙酸乙基酯、乙酸丁基酯等酯类溶剂。Examples of the organic solvent include aromatic organic solvents such as xylene, toluene, and ethylbenzene; ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Aliphatic (1-10 carbon atoms, preferably about 2-5 carbon atoms) monohydric alcohols such as alcohol and isobutanol; ester solvents such as ethyl acetate and butyl acetate.
上述溶剂(K)的含量相对于本发明的防污涂料组合物的固体成分(加热残留成分)的总量100重量％，通常为0～80重量％，优选10～60重量％。The content of the solvent (K) is usually 0 to 80% by weight, preferably 10 to 60% by weight, based on 100% by weight of the total solid content (residual heating content) of the antifouling paint composition of the present invention.
上述共聚物(A)和上述聚合物(B)的总重量相对于本发明的防污涂料组合物的固体成分(加热残留成分)的总量100重量％，优选5重量％以上，更优选10重量％以上。如果上述总重量在该范围内，则在对由含有上述溶剂的防污涂料组合物形成的涂膜进行干燥时不易发生涂膜产生裂纹等不良情况。The total weight of the above-mentioned copolymer (A) and the above-mentioned polymer (B) is preferably 5% by weight or more, more preferably 10% by weight relative to the total amount of solid content (residual heating content) of the antifouling coating composition of the present invention (100% by weight). % by weight or more. When the above-mentioned total weight is within this range, troubles such as cracks in the coating film are less likely to occur when the coating film formed from the antifouling coating composition containing the above-mentioned solvent is dried.
作为本发明的防污涂料组合物，优选例举固体成分含量为70重量％以上、在25℃条件下用斯氏粘度计测定的涂料粘度(KU值)为70～110的防污涂料组合物。As the antifouling paint composition of the present invention, preferably, an antifouling paint composition having a solid content of 70% by weight or more and a paint viscosity (KU value) of 70 to 110 as measured by a Sturdier viscometer at 25°C .
<防污涂料组合物的制造方法><Manufacturing method of antifouling paint composition>
本发明的防污涂料组合物除了使用上述共聚物(A)以及上述聚合物(B)以外，可适当利用公知的方法进行制造。例如，可以将共聚物(A)、和聚合物(B)、和根据需要使用的其他成分(例如，选自成分(C)～成分(K)的成分)一次性或以任意的顺序添加在搅拌容器中，用公知的搅拌·混合方法混合各成分，使其在溶剂中分散或溶解来进行制造。The antifouling paint composition of this invention can be manufactured by a well-known method suitably except using the said copolymer (A) and the said polymer (B). For example, the copolymer (A), the polymer (B), and other components (for example, components selected from the components (C) to (K)) used as needed can be added at one time or in any order. In a stirring vessel, each component is mixed by a known stirring and mixing method, and dispersed or dissolved in a solvent to produce it.
此外，优选在溶剂中将各成分分散或溶解后，添加酰胺蜡(例如，DISPARLON630-20X等)，使其分散(例如，通过搅拌10～20分钟左右进行分散)来制备防污涂料组合物。这样的话，在将得到的防污涂料组合物涂覆在基材上时可减少流挂的发生。In addition, after dispersing or dissolving each component in a solvent, it is preferable to add an amide wax (for example, DISPARLON 630-20X, etc.) and disperse (for example, disperse by stirring for about 10 to 20 minutes) to prepare an antifouling coating composition. In this way, the occurrence of sagging can be reduced when the obtained antifouling coating composition is applied to a substrate.
作为搅拌·混合方法，可例举高速分散机、砂磨机、篮式砂磨机、球磨机、三辊研磨机、罗斯式搅拌机(ロスミキサー)、行星式搅拌机、万能品川搅拌机等。The stirring and mixing method may, for example, be a high-speed disperser, a sand mill, a basket mill, a ball mill, a three-roll mill, a Ross mixer, a planetary mixer, or a universal Shinagawa mixer.
[防污涂料组合物的用途][Use of Antifouling Paint Composition]
本发明的防污涂膜由本发明的防污涂料组合物形成。The antifouling coating film of the present invention is formed from the antifouling coating composition of the present invention.
此外，本发明的防污基材具备基材、和设于该基材的表面上的本发明的防污涂膜。Moreover, the antifouling base material of this invention is equipped with a base material, and the antifouling coating film of this invention provided on the surface of this base material.
本发明的防污基材的制造方法，包括在基材(目的物、被涂装物)上涂覆、或使其含浸本发明的防污涂料组合物的工序，在该组合物进一步含有溶剂的情况下，还包括从涂覆或含浸于基材的涂料组合物中去除溶剂的工序。上述的涂覆中，例如可使用空气喷涂、无气喷涂、刷毛、辊等涂装方法，上述的溶剂的除去中，例如可自然干燥(即放置在室温左右的温度下)或采用加热器等加热方法。The method for producing an antifouling substrate of the present invention includes the step of coating or impregnating the antifouling coating composition of the present invention on a substrate (object, object to be coated), and the composition further contains a solvent In the case of the present invention, the process of removing the solvent from the coating composition applied or impregnated to the substrate is also included. In the above-mentioned coating, for example, air spraying, airless spraying, brushing, roller and other coating methods can be used. In the removal of the above-mentioned solvent, for example, it can be dried naturally (that is, placed at a temperature around room temperature) or using a heater, etc. heating method.
作为上述基材，没有特别的限定，优选可例举与海水或淡水接触的基材，具体而言，可例举各种发电站(火力、核能)的给排水口、湾岸道路、海底隧道、港口设备或运河、水路等各种海洋·河流土木工程中使用的污泥扩散防止膜等水中结构物、FRP船等船舶(尤其是船舶的吃水部到船底部分)、渔业物资(绳缆、渔网等渔具、浮标或救生圈等)。The base material is not particularly limited, but preferred examples include base materials in contact with seawater or fresh water. Specifically, water outlets of various power stations (thermal power, nuclear power), bay coast roads, subsea tunnels, Port facilities, canals, waterways and other marine and river constructions, underwater structures such as sludge diffusion prevention membranes, ships such as FRP ships (especially from the draft to the bottom of ships), fishery materials (ropes, fishing nets) such as fishing gear, buoys or life buoys, etc.).
作为这些基材的材质，船舶中可例举钢、铝、木材等，渔网等中可例举天然·合成纤维，浮标、救生圈等中可例举合成树脂，只要是在水中要求防污性等的基材，则对其材质没有特别限定。The materials of these base materials include steel, aluminum, wood, etc. for ships, natural and synthetic fibers for fishing nets, etc., synthetic resins for buoys, buoys, etc., as long as antifouling properties are required in water, etc. The material of the base material is not particularly limited.
如果在这些基材的表面(在基材为船底等的情况下，通常为在钢制基材的表面上底涂防锈涂料等底涂剂后的底涂剂处理基材的表面)上，通过如上所述的方法，涂覆1次或多次本发明的防污涂料组合物(防污涂料)，或在基材为渔网等情况下使本发明的防污涂料组合物(防污涂料)含浸于基材中，再根据需要除去涂覆或含浸的防污涂料组合物中的溶剂等，使其固化，形成防污涂膜，则长期防止石莼、藤壶、浒苔、龙介虫(serpula)、牡蛎、草苔虫等水生生物附着的特性(防污性，尤其是静置防污性)优良，可长期缓慢释放防污成分(例如，铜化合物(D成分)、有机防污剂(E成分))。If on the surface of these substrates (in the case where the substrate is the bottom of a ship, etc., usually the surface of a steel substrate is primed with a primer such as an antirust paint, the surface of the primer treated substrate), By the method as described above, apply the antifouling paint composition (antifouling paint) of the present invention once or multiple times, or make the antifouling paint composition (antifouling paint) of the present invention ) is impregnated in the base material, and then the solvent in the coated or impregnated antifouling coating composition is removed as required, and solidified to form an antifouling coating film, which will prevent Ulva, barnacles, Enteromorpha, and Ryusuke for a long time. It has excellent adhesion characteristics (antifouling properties, especially static antifouling properties) of aquatic organisms such as serpula, oysters, and bryozoans, and can slowly release antifouling components (such as copper compounds (component D), organic antifouling properties) for a long period of time. staining agent (E component)).
此外，在基材为船舶(尤其是其船底)、水中结构物等情况下，通常基材表面经底涂处理，有时在基材表面上具有由环氧树脂涂料、乙烯基树脂类涂料、丙烯酸树脂类涂料、聚氨酯树脂类涂料的任一种形成的层。在该基材表面上，多次涂覆(厚涂：干燥膜厚100～600μm左右)本发明的防污涂料组合物而得的防污涂膜在发挥优良的防污性的同时，可平衡性良好地发挥适度的可挠性以及优良的耐裂纹性。In addition, when the substrate is a ship (especially its bottom), underwater structures, etc., the surface of the substrate is usually treated with a primer, and sometimes the surface of the substrate is coated with epoxy resin coating, vinyl resin coating, acrylic paint, etc. A layer formed of either resin-based paint or polyurethane resin-based paint. On the surface of the substrate, the antifouling coating film obtained by applying the antifouling coating composition of the present invention multiple times (thick coating: about 100 to 600 μm in dry film thickness) exhibits excellent antifouling properties and can balance It exhibits moderate flexibility and excellent crack resistance well.
在制造上述防污基材时，基材为渔网或具有劣化了的防污涂膜的钢板的情况下，可在基材表面直接涂覆本发明的防污涂料组合物或进行含浸(渔网等情况下)，此外，在基材为钢板原坯的情况下，可以预先在基材表面上涂覆防锈剂或底涂剂等基底材料、形成基底层后，在该基底层的表面上涂覆本发明的涂料组合物。此外，可以以修补为目的，在形成有本发明的防污涂膜或以往的防污涂膜的基材的表面上进一步形成本发明的防污涂膜。When manufacturing the above-mentioned antifouling substrate, if the substrate is a fishing net or a steel plate with a deteriorated antifouling coating film, the antifouling coating composition of the present invention can be directly coated on the surface of the substrate or impregnated (fishing nets, etc.) case), in addition, in the case of the base material is the original steel plate, it is possible to coat the base material such as antirust agent or primer on the surface of the base material in advance, after forming the base layer, coat the surface of the base layer Coating composition of the present invention. In addition, for the purpose of repairing, the antifouling coating film of the present invention may be further formed on the surface of the base material on which the antifouling coating film of the present invention or a conventional antifouling coating film is formed.
对本发明的防污涂膜的厚度没有特别限定，但在基材为船舶或水中结构物的情况下，例如为30～1000μm左右。The thickness of the antifouling coating film of the present invention is not particularly limited, but when the base material is a ship or an underwater structure, it is, for example, about 30 to 1000 μm.
此外，在基材上涂覆上述防污涂料组合物、形成防污涂膜的情况下，对1次涂装所形成的防污涂膜的厚度(在上述防污涂料组合物含有溶剂的情况下，指溶剂去除后的涂膜厚度)没有特别限定，但在基材为船舶或水中结构物的情况下，例如为30～250μm左右。In addition, when the above-mentioned antifouling coating composition is coated on the substrate to form an antifouling coating film, the thickness of the antifouling coating film formed by one coating (in the case where the above-mentioned antifouling coating composition contains a solvent Hereinafter, the thickness of the coating film after solvent removal) is not particularly limited, but when the base material is a ship or an underwater structure, it is, for example, about 30 to 250 μm.
这样，由于可长期防止水棲生物对具有本发明的防污涂膜的水中结构物的附着，因此可长期维持水中结构物的功能。此外，具有本发明的防污涂膜的渔网在环境污染的可能性小的基础上，可防止水生生物的附着，因此可防止网眼的阻塞。In this way, since the attachment of aquatic organisms to the underwater structure having the antifouling coating film of the present invention can be prevented for a long time, the function of the underwater structure can be maintained for a long time. In addition, the fishing net having the antifouling coating film of the present invention can prevent the attachment of aquatic organisms and thus prevent the clogging of the mesh while reducing the possibility of environmental pollution.
实施例Example
下面基于实施例以及比较例对本发明进行更具体的说明，但本发明并不限定于以下任一实施例。另外，以下的实施例以及比较例中，“份”以及“％”分别表示“重量份”以及“重量％”。The present invention will be described more specifically based on examples and comparative examples below, but the present invention is not limited to any of the following examples. In addition, in the following examples and comparative examples, "parts" and "%" represent "parts by weight" and "% by weight", respectively.
进行相对于聚合物(共聚物)以及聚合物(共聚物)溶液的加热残留成分的含有率、粘度、GPC的测定。各测定条件如下。The content rate of the heating residual component with respect to a polymer (copolymer) and a polymer (copolymer) solution, viscosity, and GPC measurement were performed. Each measurement condition is as follows.
[加热残留成分的含有率测定条件][Measurement conditions for content rate of heating residue components]
在直径6cm的铝试验皿中量取聚合物(共聚物)溶液X1(g)，将其均匀涂开。在160℃的恒温槽内将其加热1小时去除挥发成分。量取得到的不挥发成分的重量(X2(g))，由下述式算出加热残留成分的含有率。Measure the polymer (copolymer) solution X 1 (g) in an aluminum test dish with a diameter of 6 cm, and spread it evenly. It was heated in a constant temperature bath at 160° C. for 1 hour to remove volatile components. The weight (X 2 (g)) of the obtained non-volatile matter was measured, and the content rate of the heating residue was calculated from the following formula.
加热残留成分的含有率(％)＝X2÷X1×100Content rate of heating residual components (%) = X 2 ÷ X 1 × 100
[粘度测定条件][Viscosity measurement conditions]
装置：E型粘度计(东机产业株式会社(東機産業(株)社)制)Device: E-type viscometer (manufactured by Toki Sangyo Co., Ltd. (Toki Sangyo Co., Ltd.))
测定温度：25℃Measuring temperature: 25°C
[GPC测定条件][GPC measurement conditions]
装置：HLC-8120GPC(东曹株式会社制)Device: HLC-8120GPC (manufactured by Tosoh Corporation)
柱：SuperH2000+SuperH4000(均为东曹株式会社制，6mm(内径)×15cm(长度))Column: SuperH2000+SuperH4000 (both manufactured by Tosoh Corporation, 6mm (inner diameter)×15cm (length))
溶离液：THF(四氢呋喃)Eluent: THF (tetrahydrofuran)
流速：0.500ml/分钟Flow rate: 0.500ml/min
检测器：RIDetector: RI
柱恒温槽温度：40℃Column thermostat temperature: 40°C
标准物质：聚苯乙烯Standard material: polystyrene
<制造例1(共聚物(A)的溶液的制造)><Production example 1 (production of solution of copolymer (A))>
在具备搅拌机、电容器、温度计、氮导入管以及滴加装置的反应容器中投入二甲苯66.66份，在氮气气氛下进行加热搅拌，使液温达到110℃。一边保持相同条件，一边通过滴加装置向反应容器内滴加单体类(苯乙烯50份、甲基丙烯酸缩水甘油酯10份、甲基丙烯酸甲酯15份、丙烯酸丁酯25份)和聚合引发剂(2，2'-偶氮二-2-甲基丁腈1.5份、过氧苯甲酸叔丁酯1份)的混合物3小时，接着，在相同温度下持续加热搅拌1小时、120℃下加热搅拌1小时、130℃下加热搅拌1小时后，在反应容器中加入二甲苯15.16份，得到共聚物(A)-1的溶液(以下也称“共聚物溶液(A)-1”。)。66.66 parts of xylenes were put into the reaction container equipped with the stirrer, capacitor, thermometer, nitrogen introduction pipe, and dripping apparatus, and it heat-stirred in nitrogen atmosphere, and made liquid temperature 110 degreeC. While maintaining the same conditions, monomers (50 parts of styrene, 10 parts of glycidyl methacrylate, 15 parts of methyl methacrylate, 25 parts of butyl acrylate) and polymerization A mixture of initiators (1.5 parts of 2,2'-azobis-2-methylbutyronitrile, 1 part of tert-butyl peroxybenzoate) was used for 3 hours, followed by heating and stirring at the same temperature for 1 hour, 120°C After heating and stirring at 130° C. for 1 hour and 1 hour at 130° C., 15.16 parts of xylene was added to the reaction vessel to obtain a solution of copolymer (A)-1 (hereinafter also referred to as “copolymer solution (A)-1”). ).
除了将单体类如表1所记载的进行变更以外，进行与上述相同的操作，制作其他共聚物(A)溶液(共聚物溶液(A)-2～共聚物溶液(A)-13)。其性状值示于表1。Except having changed monomers as described in Table 1, the same operation as above was performed to prepare other copolymer (A) solutions (copolymer solution (A)-2 to copolymer solution (A)-13). The property values are shown in Table 1.
表1Table 1
<制造例2(共聚物(B)的溶液的制造)><Production example 2 (production of solution of copolymer (B))>
在具备搅拌机、电容器、温度计、氮导入管以及滴加装置的反应容器中投入二甲苯53份，在氮气气氛下进行加热搅拌，使液温达到85℃。一边保持相同条件，一边通过滴加装置向反应容器内滴加单体类(三异丙基甲硅烷基丙烯酸酯60份、甲基丙烯酸甲酯40份)和聚合引发剂(2，2'-偶氮二异丁腈0.5份)的混合物4小时，接着，在相同温度下继续加热搅拌1小时后，在反应容器中加入过氧苯甲酸叔丁酯0.5份。接着，继续在液温90℃下加热搅拌1小时、100℃下加热搅拌1小时、110℃下加热搅拌1小时、120℃下加热搅拌1小时后，在反应容器中加入二甲苯28.8份，得到共聚物(B)-1的溶液(以下也称“共聚物溶液(B)-1”。)。53 parts of xylene were put into the reaction container equipped with the stirrer, capacitor, thermometer, nitrogen introduction pipe, and dripping apparatus, and it heat-stirred under nitrogen atmosphere so that liquid temperature might become 85 degreeC. While maintaining the same conditions, monomers (60 parts of triisopropylsilyl acrylate, 40 parts of methyl methacrylate) and polymerization initiators (2,2'- Azobisisobutyronitrile (0.5 parts) was mixed for 4 hours, and then, after heating and stirring at the same temperature was continued for 1 hour, 0.5 parts of tert-butyl peroxybenzoate was added to the reaction vessel. Next, after heating and stirring at a liquid temperature of 90° C. for 1 hour, 100° C. for 1 hour, 110° C. for 1 hour, and 120° C. for 1 hour, add 28.8 parts of xylene to the reaction vessel to obtain A solution of copolymer (B)-1 (hereinafter also referred to as "copolymer solution (B)-1").
除了将单体类如表2所记载的进行变更以外，进行与上述相同的操作，制作其他共聚物(B)溶液(共聚物溶液(B)-2～共聚物溶液(B)-4)。其性状值示于表2。Except having changed monomers as described in Table 2, the same operation as above was performed to prepare other copolymer (B) solutions (copolymer solution (B)-2 to copolymer solution (B)-4). The property values are shown in Table 2.
表2Table 2
表2：共聚物(B)溶液Table 2: Copolymer (B) Solutions
<防污涂料组合物的制备><Preparation of Antifouling Paint Composition>
(实施例1)(Example 1)
如下制备防污涂料组合物。The antifouling coating composition was prepared as follows.
首先，在容量1000ml的塑料容器内掺合溶剂二甲苯(14.1份)和三甲基异丁烯基环己烯羧酸(9.0份)，将其用涂料分散机搅拌直至该羧酸均匀溶解为止。在得到的溶液中添加共聚物溶液(A)-1(8.2份)、共聚物溶液(B)-1(8.2份)，搅拌至混合均匀，接着，再添加氧化锌(4.0份)、氧化亚铜NC301(44份)、萘酚红(2.5份)、钛白R-5N(1.5份)、吡啶硫酮铜(3.0份)、防沉降剂DISPARLON4200-20X(2.0份)、烧石膏FT-2(1.0份)，添加玻璃珠200份，搅拌1小时使其分散。在得到的分散液中添加防流挂剂DISPARLON630-20X(2.5份)，搅拌20分钟使其分散后，用80目的过滤网进行过滤，制备防污涂料组合物。First, the solvent xylene (14.1 parts) and trimethylisobutenylcyclohexene carboxylic acid (9.0 parts) were blended in a 1000 ml plastic container, and stirred with a paint disperser until the carboxylic acid was uniformly dissolved. Add copolymer solution (A)-1 (8.2 parts) and copolymer solution (B)-1 (8.2 parts) to the obtained solution, stir until the mixture is uniform, then add zinc oxide (4.0 parts), nitrous oxide Copper NC301 (44 parts), naphthol red (2.5 parts), titanium dioxide R-5N (1.5 parts), copper pyrithione (3.0 parts), anti-settling agent DISPARLON4200-20X (2.0 parts), calcined gypsum FT-2 (1.0 part), 200 parts of glass beads were added, and it stirred for 1 hour and was dispersed. The anti-sagging agent DISPARLON630-20X (2.5 parts) was added to the obtained dispersion, stirred for 20 minutes to disperse, and then filtered through an 80-mesh filter to prepare an antifouling coating composition.
(实施例2～18)(Examples 2-18)
除了如表3所示改变掺和量以及共聚物溶液的种类以外，以与实施例1相同的方式制备防污涂料组合物。An antifouling coating composition was prepared in the same manner as in Example 1 except that the blending amount and the kind of the copolymer solution were changed as shown in Table 3.
表3table 3
(比较例1～6)(Comparative examples 1 to 6)
除了如表4所示改变掺和量以及共聚物溶液的种类以外，以与实施例1相同的方式制备防污涂料组合物。An antifouling coating composition was prepared in the same manner as in Example 1 except that the blending amount and the kind of the copolymer solution were changed as shown in Table 4.
表4Table 4
表4：比较例配方表Table 4: Comparative Example Formulation Table
另外，实施例以及比较例所使用的成分的详情如下。In addition, the details of the components used in Examples and Comparative Examples are as follows.
表5table 5
<防污涂料组合物的物性评价><Evaluation of Physical Properties of Antifouling Paint Composition>
对实施例1～18以及比较例1～6的防污涂料组合物以及使用它们而形成的涂膜的物性进行如下评价。所得结果示于表6。The physical properties of the antifouling paint composition of Examples 1-18 and Comparative Examples 1-6, and the coating film formed using them were evaluated as follows. The obtained results are shown in Table 6.
(1)涂料粘度测定(1) Measurement of paint viscosity
根据JISK-5600-2-2的规定用斯氏粘度计进行测定。The measurement was carried out with a Student's viscometer in accordance with JIS K-5600-2-2.
斯氏粘度计：涂料试验机工业株式会社(コーティングテスター工業)制斯氏粘度计SS Viscometer: SS Viscometer manufactured by Coating Tester Industry Co., Ltd.
设定温度：25℃±0.5℃Set temperature: 25℃±0.5℃
样品量：500mlSample size: 500ml
砝码：75g～1000gWeight: 75g～1000g
(2)防污涂膜的加速劣化试验(2) Accelerated deterioration test of antifouling coating film
在150×70×1.6mm的喷砂处理钢板上，每天依次涂装干燥膜厚达到150μm的环氧类涂料(中国涂料株式会社(中国塗料(株))制“BANNOH500”)、干燥膜厚达到100μm的环氧类粘合剂涂料(中国涂料株式会社制“BANNOH500N”)，之后在该由环氧类粘合剂涂料形成的涂膜的表面上涂覆实施例或比较例所制备的防污涂料组合物，使其干燥膜厚达到150μm，制成试验板。每1种防污涂料组合物制作2块试验板。On a blasted steel plate of 150×70×1.6 mm, epoxy-based paint ("BANNOH500" manufactured by China National Paint Co., Ltd. 100 μm epoxy-based adhesive paint ("BANNOH500N" manufactured by China National Paint Co., Ltd.), and then apply the antifouling prepared in Examples or Comparative Examples on the surface of the coating film formed by the epoxy-based adhesive paint. The coating composition was made to have a dry film thickness of 150 μm, and a test panel was prepared. Two test panels were prepared for each antifouling paint composition.
将上述试验板在23℃下干燥7天，将1块试验板浸渍在50℃的天然海水中，另1块试验板浸渍在50℃的自来水中，每1个月分别调查涂膜外观，实施4个月。另外，每周更换新鲜的天然海水以及自来水。Dry the above-mentioned test panels at 23°C for 7 days, immerse one test panel in natural seawater at 50°C, and immerse the other test panel in tap water at 50°C, and investigate the appearance of the coating film every month. 4 months. In addition, fresh natural sea water and tap water are replaced every week.
对于涂膜的裂纹，使用在50℃的海水中浸渍后的试验板，根据JISK5600-8-4进行评价，对于起泡，使用在50℃的自来水中浸渍后的试验板，进行目测评价。Cracks in the coating film were evaluated according to JIS K5600-8-4 using a test panel immersed in 50° C. seawater, and visual evaluation was performed using a test panel immersed in 50° C. tap water for blistering.
评价标准：evaluation standard:
<裂纹性><cracking>
0/放大10倍也不能看出0/10 times magnification can not be seen
1/放大10倍则可看出1/10 times magnification can be seen
2/在矫正到正常的视力下可以勉强看出2/ Can barely see with corrected to normal vision
3/在矫正到正常的视力下可以明显看出3/ Visible under corrected to normal vision
4/通常有达到宽1mm的较大破裂4/Usually there are larger cracks up to 1mm wide
5/通常有超过宽1mm的很大破裂5/ Usually there are large cracks exceeding 1mm wide
<起泡性><Foaming>
0/外观无异常0/ Appearance is normal
1/存在1～5个起泡1/ There are 1 to 5 blisters
2/存在5个以上起泡2/ There are more than 5 bubbles
(3)静置防污性试验(3) Static antifouling test
在150×70×3.2mm的喷砂处理钢板上，每天依次涂装干燥膜厚达到150μm的环氧类涂料(中国涂料株式会社制“BANNOH500”)、干燥膜厚达到100μm的环氧类粘合剂涂料(中国涂料株式会社制“BANNOH500N”)，之后间隔1天，在该由环氧类粘合剂涂料形成的涂膜的表面上涂覆实施例或比较例所制备的防污涂料组合物，使其干燥膜厚达到150μm，制成试验板。On a 150×70×3.2mm sandblasted steel plate, apply epoxy-based paint with a dry film thickness of 150 μm ("BANNOH500" manufactured by China National Paint Co., Ltd.) and epoxy-based adhesive with a dry film thickness of 100 μm every day. adhesive coating ("BANNOH500N" manufactured by China National Paint Co., Ltd.), and then at intervals of 1 day, the antifouling coating composition prepared in the examples or comparative examples was applied on the surface of the coating film formed by the epoxy adhesive coating , so that the dry film thickness reaches 150 μm, and a test plate is made.
将上述试验板在23℃下干燥7天，静置浸渍在长崎县长崎湾中，每1个月通过目视计测附着生物的附着面积，基于下述评价基准进行评价。The said test plate was dried at 23 degreeC for 7 days, it was left still and immersed in Nagasaki Bay, Nagasaki Prefecture, and the adhesion area of the fouling organisms was visually measured every month, and it evaluated based on the following evaluation criteria.
<评价基准><Evaluation criteria>
0：没有水生生物附着0: No aquatic life attached
0.5：水生生物的附着面积超过0％且在10％以下0.5: The attachment area of aquatic organisms is more than 0% and less than 10%
1：水生生物的附着面积超过10％且在20％以下1: The attachment area of aquatic organisms exceeds 10% and is less than 20%
2：水生生物的附着面积超过20％且在30％以下2: The attachment area of aquatic organisms exceeds 20% and is less than 30%
3：水生生物的附着面积超过30％且在40％以下3: The attachment area of aquatic organisms exceeds 30% and is less than 40%
4：水生生物的附着面积超过40％且在50％以下4: The attachment area of aquatic organisms exceeds 40% and is less than 50%
5：水生生物的附着面积超过50％5: The attachment area of aquatic organisms exceeds 50%
(4)涂膜消耗性(4) Coating film consumption
将实施例以及比较例所得到的各防污涂料组合物以使干燥膜厚为150μm的方式用分配器涂覆在硬质氯乙烯基板(50mm×50mm×1.5mm)，使其干燥，制作试验板。Each antifouling paint composition obtained in Examples and Comparative Examples was coated on a rigid vinyl chloride substrate (50 mm x 50 mm x 1.5 mm) with a dispenser so that the dry film thickness was 150 μm, and dried to prepare a test plate.
将得到的试验板安装在旋转鼓上，将该旋转鼓浸渍在海水中，在海水温度30℃的条件下以周速15节使其旋转，测定每1个月的消耗膜厚。此外，观察浸渍开始12个月后的涂膜外观，基于下述评价基准进行评价。The obtained test panel was mounted on a rotary drum, and the rotary drum was immersed in seawater, and rotated at a peripheral speed of 15 knots under the condition of a seawater temperature of 30° C., and the consumed film thickness every month was measured. Moreover, the external appearance of the coating film 12 months after the start of immersion was observed, and it evaluated based on the following evaluation criteria.
评价基准：外观○/外观无异常Evaluation Criteria: Appearance ○ / No abnormality in appearance
×/产生裂纹×/ crack
表6Table 6
表7Table 7
表8Table 8
表6：各性能评价一览(续)Table 6: List of performance evaluations (continued)
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| CN114702618A (en) * | 2022-04-15 | 2022-07-05 | 哈尔滨工程大学 | Indoleacetic acid-modified acrylic fluoropolymer and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| US9976040B2 (en) | 2018-05-22 |
| CN105143368B (en) | 2017-08-04 |
| US20170015841A1 (en) | 2017-01-19 |
| KR101712761B1 (en) | 2017-03-06 |
| JP5989237B2 (en) | 2016-09-07 |
| WO2014175246A1 (en) | 2014-10-30 |
| EP2990449B1 (en) | 2017-06-28 |
| AR096059A1 (en) | 2015-12-02 |
| SG11201508319QA (en) | 2015-11-27 |
| MY176309A (en) | 2020-07-28 |
| JPWO2014175246A1 (en) | 2017-02-23 |
| EP2990449A4 (en) | 2016-12-14 |
| KR20150138354A (en) | 2015-12-09 |
| BR112015026577A2 (en) | 2017-07-25 |
| EP2990449A1 (en) | 2016-03-02 |
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